Methods and systems for the quantitative chemical speciation of heavy metals and other toxic pollutants

ABSTRACT

This invention relates to systems and methods for measuring quantitatively multiple species or heavy metals, including mercury, and other toxic pollutants. More specifically, the systems and methods of the invention allows for determination of the analytes even at very low concentration, through concentration on a collection interface, desorption and analysis by mass spectrometry. The invention also provides for a portable device or kit for modifying an existing mass spectrometer.

FIELD OF THE INVENTION

The invention relates generally to methods, systems and portable devicesfor measuring quantitatively multiple species of heavy metals, includingmercury or other toxic pollutants in air, and in the aqueous phase,including water, molten snow/ice, and rain.

BACKGROUND OF THE INVENTION

Mercury is the top-identified contaminant in the environment and hasbeen identified as a toxic agent by international advisory boards. It isthe one metal that is least effectively retained by emission controls,partly due to its high vapour pressure. Once emitted, mercury may bedeposited by wet and dry processes to environmental surfaces. In itsvapour form, mercury can be carried long distances on wind currents,staying in the atmosphere for long periods of time. Mercury can changefrom one form to another in the environment (FIG. 1). For example, sometypes of bacteria and fungi can change mercury into its most toxic form,methyl mercury. Methyl mercury tends to be bio-magnified, accumulatingto some degree in all fish, but especially in predatory fish such asshark, swordfish and large tuna, as well as in marine mammals. Mercuryis also leached from flooded soil at new hydroelectric dam sites, orfrom any flooded area. This process can add to mercury levels infreshwater aquatic food chains in those areas. The health effects ofmercury exposure depend on its chemical form (elemental, inorganic ororganic), the route of exposure (inhalation, ingestion or skin contact),and the level of exposure. Vapour from liquid elemental mercury andmethyl mercury is more easily absorbed than inorganic mercury salts andcan therefore cause more harm.

Therefore knowledge of the different forms or speciation of atmosphericmercury is crucial for predicting its deposition and understanding itsbiogeochemical cycling. Presently the current techniques provideinformation on elemental analysis and the chemical composition ofmercury species cannot be determined in detail. Mercury speciationmeasurement is one of the most important challenges. The currentinability to measure multiple mercury species constitutes a major gap inthe understanding of mercury cycling and precludes adequate conclusionsby scientists and policymakers alike [1]. Presently, existing analytictechniques for atmospheric mercury only provide information on (a) totalmercury; (b) elemental mercury, (c) particulate mercury, and (d) anoperationally (but not chemically) defined group called reactive gaseousmercury (RGM). The detailed chemical characterization of RGM isessential in understanding properties such as solubility,gas-to-particle partitioning, as well as processes such asbiomagnification and bio-accumulation in aquatic systems. Currently, themajor mercury detection systems include a gold trap used in connectionwith cold-vapour fluorescence units or atomic absorption units formercury analysis. Using these techniques, one can obtain total mercuryconcentrations, as well as accurate elemental mercury concentrations.However, obtaining accurate concentration of mercury-containingmolecular species is currently not possible. Therefore, there is a needfor a method and device that identifies and quantifies the manydifferent species of mercury in air and aqueous systems.

SUMMARY OF THE INVENTION

The present invention reduces the aforesaid difficulties anddisadvantages. The present invention provides methods, systems andportable devices for the identification and quantification of mercuryspecies and other metal species (e.g. heavy metal species) in air and inaqueous systems, as well as in ice and snow.

According to one aspect, the invention relates to a method foridentifying and quantifying metal species, for example, heavy metalspecies (e.g. mercury (e.g. HgBr₂, HgO, Hg(OH)₂, HgCl₂, CH₃HgCl, and thelike), lead, arsenic, cadmium, zinc, and the like), in a sample (e.g.air, water, snow, ice, and the like), comprising the steps of: a)collecting the sample onto a collection interface thereby concentratingan analyte; b) desorbing the analyte; and c) identifying and quantifyingthe analyte's content in metal species by atmospheric pressure softionization mass spectrometry.

In one embodiment, step (a) of the method of the invention comprisesadsorbing the analyte onto the collection interface, e.g. by forming anamalgam, or by physical or physicochemical adsorption. In oneembodiment, the collection interface of step (a) comprises particles,microparticles, nanoparticles, or beads coated with the same, as well asbeads, wire, and the like, in a tube (e.g. glass, stainless steel, andthe like). Examples of collection interfaces include, withoutlimitation, gold particles, nanoparticles, gold-microparticle-coatedglass beads (e.g. quartz beads), gold wire, sulphur-containing coatednano and microparticles, polysulfide-polysilanized glass beads (e.g.quartz beads), or uncoated glass beads (e.g. quartz, Pyrex™ and thelike). The collection interface of step (a) may further comprise aheating option, such as a nichrome wire for controlling the temperatureand for the desorbing step (b).

In another embodiment, step (a) comprises passing the sample through thecollection interface at the flow rate of about 0.5 L/min to about 10L/min, preferably about 0.8 L/min to about 5 L/min, more preferablyabout 0.8 L/min to about 1.5 L/min, most preferably about 1 L/min±0.20L/min.

In another embodiment, the method further comprises passing the analytefrom step (b) through a flow through a flow tube until it reaches theproximity of a detector of a mass spectrometer. In a further embodiment,the atmospheric pressure soft ionization mass spectrometry (APSI-MS) isatmospheric pressure chemical ionization mass spectrometry (APCI-MS). Inone embodiment, the carrier gas for chemical ionization is nitrogen orisobutane-containing nitrogen, preferably nitrogen containing from about0.01% to about 2% isobutane, from about 0.05% to about 1% isobutane,from about 0.05% to about 0.5% isobutane, from about 0.08% to about 0.2%isobutane, or about 0.1% isobutane.

In a yet another embodiment, all surfaces exposed to the analyte sampleare inactivated or made of inactive material to prevent loss of analytespecies. Examples of inactivation include halocarbon wax, silanization,and Teflon™ coating. Alternatively, some parts may be made out of aninactive material such as Teflon™ or glass covered Teflon™.

Another aspect of the invention relates to a system or apparatus for usein performing the method of the invention, the system comprising atleast one collection interface as defined above, optionally including aheating option, an inlet end being optionally controlled by a flowvalve, and optionally containing a filter or multistage size-aggregatedfilters. The system also further comprises a flow tube connecting anoutlet end of the collection interface to an inlet of an atmosphericpressure soft ionization mass spectrometer detector such as (atmosphericpressure) chemical ionization, or electrospray options. The systemcomprises inactivated inner walls for preventing loss of analytespecies, or alternatively comprises means for doing so.

In yet another aspect, the invention relates to a method for modifying aMS apparatus in order to perform the method of the invention, suchmethod comprising inactivating the surfaces contacting the sampleanalyte, such as flow tubes, inlet walls, and interior of MS. The methodfurther comprise adding a concentration or collection interface asdefined above, and reducing the dead volume inside the injector port ofthe MS apparatus.

In a further aspect the invention relates to a portable device or a kitfor modifying an existing MS apparatus in order to perform the method ofthe invention, the kit comprising a one or more collection interface,flow valve(s) and tube(s) for connecting to an interface inlet, flowtube(s) for connecting from an interface outlet to an APSI-MS detectorinlet, means or instructions for inactivating/passivating inner surfacesof the device and APSI-MS, and means for reducing the dead volume insidethe injector port of the MS apparatus.

BRIEF DESCRIPTION OF THE DRAWINGS

Further aspects and advantages of the present invention will becomebetter understood with reference to the description in association withthe following drawings in which:

FIG. 1 is a schematic view of mercury in the environment.

FIG. 2 is a simplified schematic of the device of the present invention.

FIG. 3 is a simplified schematic representation of an exemplaryconfiguration for mercury analysis.

FIG. 4 is an example of a nanoparticle-coated interface produced.

FIGS. 5 a and 5 b shows a comparison of HgCl₂ mass spectra obtained withAC-APCI-MS (a) and DC-APCI-MS (b) with isobutane as a chemicalionization (CI) gas.

FIG. 6 shows the APSI-MS source for gas analysis.

FIG. 7 is a graph showing instrument sensitivity to a HgCl₂-saturatedgas stream as a function of the gas flow rate.

FIGS. 8 a and 8 b are MS spectra showing collection of HgCl₂ onto goldmicroparticles, and thermal desorption.

FIGS. 9 a to 9 d are MS spectra showing trapping of HgCl₂ onquartz-beads, followed by thermal desorption.

FIG. 10 is an example of the desorption of HgBr₂ collected from airusing gold nanoparticles exposed to ambient air for 14 hours. Nitrogenwas used as a reagent and carrier gas.

FIG. 11 shows a blank of APCI-MS with 0.1% isobutane in nitrogen as thechemical ionization (CI) gas.

FIG. 12 a shows the APCI-MS analysis of a saturated HgO(aq) solution atpH=7 (˜1 nmol HgO) where HgO/Hg(OH)₂ detected by positive ionizationAPCI-MS. FIG. 12 b shows the APCI-MS analysis of ˜50 nmol HgCl₂ (inmethanol).

FIG. 13 shows the comparison of El-MS and APCI-MS for retention of themolecular ion HgBr2.

FIG. 14 a, b, and c show some examples of real mercury speciation inrange of detection of <20 ppt: a) HgBr₂, b) Oxygenated mercury compounds(HgO/Hg(OH)₂) complexes in aquatic media, c) Blank samples for pure air;several blanks including N₂ and He were used.

DETAILED DESCRIPTION OF THE INVENTION

This invention is not limited in its application to the details ofconstruction and the arrangement of components set forth in thefollowing description or illustrated in the drawings. The invention iscapable of other embodiments and of being practiced or of being carriedout in various ways. Also, the phraseology and terminology used hereinis for the purpose of description and should not be regarded aslimiting. The use of “including”, “comprising”, “having”, “containing”,or “involving” and variations thereof herein, is meant to encompass theitems listed thereafter as well as, optionally, additional items. In thefollowing description, the same numerical references refer to similarelements. In the drawings, like reference characters designate like orsimilar parts.

A method of identifying and quantifying metal species in air or liquidsamples according to an embodiment of the invention is described hereinwith reference to mercury species in air and liquid samples. However, itwill be appreciated that the present invention can also be applied tometals other than mercury.

An example of a system to be used in the method of the invention isshown in FIG. 2 as a simplified representation. In this system (1), forexample, air is passed through a sample inlet (2), its flow beingregulated by a meter (3). The air sample (4) may go directly through tothe interface inlet (5) or may as total mercury (6) go to the

Cold Vapor Atomic Fluorescence Spectrometer (7) (CVAFS), where totalmercury is measured. The sample then comes out as size-aggregatedparticulate mercury (8) to pass through a size-aggregated filter(s) (9)to separate aerosols, exiting as a sample (10) containing gaseousmercury compounds, the particles having been collected on the filter(s).

Analyte from either samples coming out of the interface inlets (5) arethen collected on an interface (11) comprising particles (12) inside aflow tube (13). The analyte is collected and concentrated on theparticles either by simple physical or physicochemical adsorption or bythe formation of an amalgam, depending on the particles used. Optionallya heating option (14) is fitted around the collection interface to helpdesorption of the analyte.

After desorption, the analyte comes out the interface outlet (15) to theinlet (16) of the mass spectrometer (17). The inlet (16) is situatedproximate to the ionization electrode (18) and charged collector to MS(19) to reduce the dead volume. The pumping unit (20) used in the methodof the invention is also shown in FIG. 2.

Another schematic representation of a system for use in the method ofthe invention is shown in FIG. 3, where multiple types of interfaces andcontrol valves are used. This way, samples going through path (a) willbe collected on both a mercury adsorption interface (e.g. gold, metalsand metal oxides, as well as sulfur containing compounds) as well asglass beads to facilitate desorption to mass spectrometry;

samples going through path (b) will be collected on a mercury adsorptioninterface alone; samples going through path (c) will be collected on aglass bead interface (to adsorb all adsorbing pollutants in diluentsfluid); samples going through path (d) are injected directly withoutbeing collected; and samples going through path (e) are adsorbed on agold interface with and without pyrolysis using a cold-vaporfluorescence detector (CVAFS) as an analytical comparison, and thustotal mercury, elemental mercury particulate and some oxidized mercurydata can be obtained. It is of note that the CVAFS does not provideadequate detailed chemical speciation for oxidized mercury species thatmass spectrometry options can provide. Each sample path is controlledvia an independent valve such that only one sample is analyzed at thetime. Results of the analysis through the mass spectrometer for eachindividual path are compiled in the computer system to identify andquantify each mercury species present in the original air or watersample.

The Mass Spectrometer used for the method of the invention is,preferably, a modified atmospheric pressure soft ionization massspectrometer (APSI-MS). The soft ionization mass spectrometer can be anatmospheric pressure chemical ionization mass spectrometer (APCI-MS) forair samples or an electrospray ionization mass spectrometer (EI-MS),preferably an atmospheric pressure chemical ionization mass spectrometer(APCI-MS).

The collection interface for use in the methods and systems of theinvention generally comprises particles, microparticles, nanoparticles,or beads coated with the same, as well as beads, wire, and the like, ina tube (e.g. glass, stainless steel, and the like). For example, thecollection interface comprises, without limitation, gold particles (e.g.microparticles, nanoparticles, and the like), gold-particles-coatedbeads or wire (e.g. glass beads such as quartz beads, or stainlesssteel, iron or copper beads or wire), gold wire,polysulfide-polysilanized beads or wire (e.g. glass beads such as quartzbeads, or stainless steel, iron or copper beads or wire), uncoated glassbeads (e.g. quartz, Pyrex™ and the like), or a combination thereof.

In one example, the use of gold nanoparticles in the interface increasesthe surface area significantly and thereby improves the sensitivity.Both gold and sulfur coated metal nanoparticles can be used as well aspure gold nanoparticles. These molecules provide strong chemicalattraction with mercury compounds and hence are adequate for binding.

Surprisingly, the use of uncoated glass beads, such as quartz beads,also provides for a good analyte collection and concentration in theinterface, as well as a smooth desorption with negligible or nopoisoning of the sample.

The use of a mercury adsorbing interface followed by a glass beadsinterface such as path (a) of FIG. 3, will particularly facilitatedesorption of mercury compounds and differential adsorption of gaseouselemental mercury and gaseous oxidized mercury.

The heating option adapted for the collection interface may be, forexample, a nichrome wire, or any other controllable heating means knownto the skilled in the art.

The following modification to the APSI-MS have also been made to thesystem: the inlet compartment, the flow system and all connection tubingand interface walls have been coated with a coating or deactivationagent, or replaced by unreactive equivalent parts to decrease the lossesand potential side reaction of mercury compounds inside the instrumentitself. The dead-volume inside the injector inlet of the APSI-MS hasbeen decreased to increase the sensitivity of the instrument. Thistechnique is recyclable, and is designed to be environmentally benign.

From one aspect, the invention consists of a portable flow-system devicewhich includes a collection interface, e.g. gold/sulphur-containingnanoparticle-based substrate or glass beads for analytecapture/adsorption. The device can be directly mounted on a massspectrometer to obtain both qualitative and quantitative chemicalspecies data for mercury in an air stream. Alternatively, the device canbe used to collect samples directly from the air stream exiting a plantstack then be removed and attached to a mass spectrometer for sampleanalysis. Optionally, the portable device comprises multiple interfacesand valves as described above and/or multistage filter, for thoseinterested in particulate chemical speciation analysis.

Advantageously, the present invention provides quantification forvarious mercury species including compounds such as HgBr₂, HgO, Hg(OH)₂,HgCl₂ in gas phase and condensed phases (e.g., air, aerosols, clouds,ice, snow and water). None of the existing commercial techniques leadsto detailed and quantifiable mercury speciation under atmosphericconditions. The time resolution of the present invention is superior orcomparable with all current techniques that do not provide such chemicalspeciation.

The portability of the device, together with its unique enablement ofmercury speciation (both qualitative and quantitative), points toapplications ranging from coal-based electricity generating plants torefineries (oil, aluminum), through to hydro-electric utilities.

EXAMPLES Example 1 Preparation of the System

a. Preparation of Gold Nanoparticle-coated Fiber and Trap

Single layer Au-nanoparticle surfaces are coated onto stainless-steelinterface and/or a wire for mercury capture. The process begins bycleaning the stainless-steel wire with a 3:1 mixture of concentratedH₂SO₄ and 30% H₂O₂, both to remove trace organics and other contaminantsand to increase the number of pendant oxygen atoms available forsilanization on the surface. The cleaned wire was then immersed for twominutes in a solution containing 60 μL of3-(aminopropyl)-trimethoxysilane (APTMS) dissolved in 15 mL of a 3:1 mixof 18.2 MΩ water and ethanol. After silanization, loose silanes wereremoved from the surface by rinsing with ethanol, and thewire/filter/trap was blown-dry with UHP N₂ gas. The APTMS was allowed tocure at room temperature for several hours before continuing the SPMEpreparation.

Once the APTMS-covered wire had cured, it was immersed in a goldnanoparticle colloidal solution for 15 minutes, under agitation. Theelectrostatic attraction between pendant amines on the silane film andgold nanoparticles results in a fine coating of gold on the surface.

In addition to pure gold, we have deployed traps using elemental sulfuras well as coated iron and copper nanoparticles. 2 g of 1:1 elementalsulphur: support were used. Sorbent was preconditioned under N₂ at 400°C. for 6 hours. Bis-[3-(triethoxysilyl) propyl] tetra-sulfide] (“S4”)was also coated onto copper-doped iron or copper oxide nanoparticles. Anexample of a collection interface is shown in FIG. 4.

b. Deactivation of all Surfaces (Inlet, Flow Tube, Internal MS Surfaces,Connectors)

Inactivation of all surfaces exposed to analyte sample, that is, wallsof inlet, flow tube, interior of MS, was performed to preclude the lossof analyte species prior to mass-based separation of species. Theinterior wall of the flow tube, the interface containing nanoparticles(FIG. 4), the connections to the MS as well as the interior of the inletcompartment of the mass spectrometer were deactivated by means ofsilylation and halocarbon wax coating techniques that were described indetail elsewhere [2, 3]. This reduces the mercury loss on the surfaces,while also reducing the undesired side reactions which interfere withaccurate quantification of the mercury species.

More specifically regarding the APCI-MS inlet, thestainless-steel-and-glass APCI-MS inlet was first replaced with a 10 mLTeflon™ cell to ameliorate analyte retention in the ionization source,by removing scavenging surfaces and by focussing the analyte-rich gasstream into the ionizing corona surrounding the high-voltage dischargepin in the APCI source. However, static build-up was observed on theinner surfaces of the Teflon™ cell during operation of the high-voltagedischarge pin, resulting in deflection of the surrounding corona out ofthe path of the gas stream and complete loss of APCI-signal.

The Teflon™ cover of the cell may be replaced with an analogous covermade of quartz. However, this has the potential to scavenge analyteduring analysis. In fact, using this quartz cover, the APCI signal wasinconsistent and the corona was prone to disappear if the discharge pinwere not held at maximum voltage (4 kV).

We note that the Teflon™ cell (with glass cover) does improve instrumentsensitivity by an order of magnitude, from a S/N of ˜10 for HgCl₂ withthe original APCI configuration to a S/N of ˜100 when using the Teflon™cell. The static electricity problem was solved through the applicationof AC current to the discharge pin, as described below.

Surface passivation of the original APCI inlet with halocarbon wax or bysilanization were tested. Halocarbon wax required only dissolution insolvants such as acetone for application onto the surfaces of the APCIinlet, followed by evaporation of the acetone overnight at 150° C. Adisadvantage of the halocarbon wax is the outgas of chlorine gas intothe APCI source, resulting in the formation of CI ions which complexwith molecular ions produced from the analyte, resulting in mixedhalides (e.g. [HgBr₂Cl]⁻) which could prevent the positiveidentification of the specific chemical form of atmospheric oxidizedmercury species.

Metal and glass surfaces in the APCI source were silanized withdichloromethylsilane (DCDMS) by immersion overnight in a 5% DCDMS inethanol solution followed by curing for several hours at 150° C. Initialresults indicated that there was little or no change in scavenging ofoxidized mercury by the silanized-APCI inlet (vs. non-silanized inlet).

c. Modifying Coronal Discharge

As mentioned above, the APCI-signal using the glass-covered Teflon™ cellwas less consistent and prone to shortage. To prevent static build-up,the DC voltage source of the APCI-MS instrument was replaced with acustom-made 60 Hz AC source that supplies the same voltage range.Negative static that would normally accumulate on the Teflon™ surfacesand deflect the negative ion corona is instead neutralized during thepositive cycle of the discharge pin. Initial tests with isobutane and anAC voltage applied to the discharge pin show retention of the analyte asboth molecular ion (and the [M+C₂H₂]⁻ ion with somewhat lower signalwhen compared to the DC voltage APCI-MS (7×106 cts vs. 3×108 cts)). Thismay be due to the incomplete conversion of the analyte to the acetylenecomplex seen in DC-APCI-MS. Regardless, the S/N ratio for both methodsis comparable (S/N-1000). As an added benefit, the glass cover may bereplaced with its Teflon™ counterpart when using AC-APCI-MS, removingthe last potential surface for scavenging of analyte introduced into theAPCI source. FIG. 5 shows a comparison of HgCl₂ mass spectra obtainedwith AC-APCI-MS (a) and DC-APCI-MS (d) with isobutane as a chemicalionization gas. The larger signal for DC-APCI-MS may reflect a moreeffective conversion of the molecular ion to the [M+C₂H₂]⁻ ion(m/z=298).

d. Decreasing the Dead Volume Inside the Injector Port

Significantly decreasing the dead volume inside the inlet enablesidentification of different mercury species, as it minimizes mercuryloss inside the inlet. In order to increase the sensitivity of the massspectrometry signals for mercury containing compounds, we have used adeactivated tube bringing the flow to the vicinity of charged collectorto mass spectrometer, and thus reducing the dead volume (see FIG. 6).

e. Initial Systems Response Test

To test the sensitivity of the APCI-MS instrument to HgX₂, isobutanechemical ionization (CI) gas was passed through the HgCl₂-saturatedflask to the glass-covered Teflon™ cell and APCI-source. The flow rateof the CI gas was modulated to increase/decrease the quantity of analyteentering the cell per unit time. The response of the instrument wasroughly linear up to 0.5 L/min, after which the sensitivity of theinstrument appeared to increase significantly (FIG. 7).

The observed nonlinearity of the instrument may result from the smallvolume of the Teflon™ cell (10 mL) combined with the critical-flow rate(−0.8 L/min) across the charged cone used to collect ions into the massspectrometer for detection. Below this critical flow rate, the evacuatedsection behind the charged cone may reduce the internal pressure of theTeflon™ cell, lowering the ion density in the corona and decreasing theionization of the analyte. Increasing the flow rate to ˜0.8 L/min orabove restored the instrument to a “true” APCI-MS analysis. All furtheranalyses were held at 1 L/min to retain the high sensitivity to HgX₂observed in this study. Also of note is that a signal of 10⁸ for aHgCl₂-saturated gas stream at 1 L/min with a baseline noise of 10⁴ cts,provides a method detection limit of ˜7 pg HgCl₂. Thus, for optimalanalysis, the oxidized mercury from at least 1-2 m³ of air should becollected for detection and quantification.

Example 2 Analyte Collection for Sample

a. Example of Collection Using a Sampling Flask as an Interface

Gold and/or sulfur nanoparticle-coated surfaces (e.g. Fe/Au) werepreconditioned for several minutes under vacuum at a temperature of ca.360° C. before insertion into a ˜2 L air sampling flask. The samplingflask, as well as all FEP tubing up-flow of the flask, was washedseveral times with 1M nitric acid and 18.2 MΩ water. Air was passedthrough the air sampling flask at ca. 18 L per minute for a total timeof 14-19 hours. In one extraction, a 0.45 μm Teflon™ filter was attachedat the sample line inlet to prevent particulate mercury from enteringthe sample line.

b. Analyte Pre-concentration from Air

A series of physical and physicochemical traps for the collection ofmeasureable quantities of oxidized mercury from large volumes of airhave been developed. For example, traps included pieces of 10 cm long 6mm diameter glass tubing containing gold-microparticle-coated quartzbeads, uncoated quartz beads, gold wire, or polysulfide-silanized quartzbeads, as well as a 10 cm long 6 mm diameter empty stainless-steel tube.Nichrome wire was wrapped around each trap to provide aneasily-controllable heating source for desorption of analytes into theAPCI-MS.

Gold-microparticle-coated glass beads were capable of removingapproximately 80% of incoming HgCl₂ in a saturated gas stream (FIG. 8).Initial desorption tests indicated that the HgCl₂ decomposed attemperatures necessary for destabilization of the mercury-gold amalgam,resulting in a lower yield from the trap. Total ion count (TIC) for themass spectrum is shown in the lower panel of FIG. 8. The trappingefficiency of HgCl₂ is approximately 80%.

In another example, uncoated glass beads collected HgCl₂ from a 1 L/minstream of HgCl₂-saturated gas. The collected HgCl₂ was recovered duringthermal desorption, as both [HgCl₂]⁻ and [HgCl₂+C₂H₂]⁻. The desorptionpeak observed for mass 307 ([HgCl₃]⁻) upon heating was not observedpreviously in the run, and may indicate some thermal decomposition maybe occurring. Desorption as lower temperature may reduce thisphenomenon. HgCl₂ collection was in the order of 90%, and was recoveredin the detector as both the molecular ion and acetylene complex (seeFIG. 9).

Also, as the collection of HgX₂ by uncoated glass beads is by physicaladsorption only (as opposed to the mercury amalgamation that occurs withgold), mercury species may in competition with other low volatilitycompounds in air. Collection of HgX₂ at elevated temperature (−50° C.)may reduce the competitive adsorption of other compounds by the trap.

Example 3 Calibration and Analysis

a. APCI-MS Analysis of Mercury Species Extracted from Air

Mercuric halides collected onto gold nanoparticles-coated fibers andtraps were desorbed directly into the source of an atmospheric pressurechemical ionization mass spectrometer (APCI-MS) for detection. APCI-MSanalysis of mercury halides is performed in negative mode (i.e.detection of negative ions only). The APCI-MS inlet accommodates boththe fiber and a N₂ carrier gas that flows around the outer tubing of thefiber at a rate of 0.3-3 L/min. Initially, the inlet is kept isothermalat 50° C. while the fiber is exposed to the gas stream. No gases areobserved to desorb from the fiber/trap at this temperature. When theinstrument baseline is stable, the inlet is ramped to 360-375° C. overthe course of several seconds. The HgCl₂ and HgBr₂-gold amalgamsdestabilize in the temperature range of 300-330° C., resulting in a peakwhose area can be integrated for quantification similar to thechromatograms obtained by gas chromatography. FIG. 10 is an example ofthe desorption of HgBr₂ collected from air using gold nanoparticles.

The APCI-MS normally utilizes nitrogen as a reagent gas to ionizeanalytes in the corona discharge in the ion source. Excess energy afterionization of mercury halides results in fragmentation of the molecularions and formation of mixed halides such as HgBr₂Cl. This preventsdirect identification of the chemical species of mercury collected ontothe SPME fiber. An alternative reagent gas is isobutane, which preservesmolecular ions through complexation as [M+26]⁻. The negative modeAPCI-MS analysis of isobutane shows the presence of a fraction atm/z=26, which is presumably C₂H₂ ⁻, although tandem MS investigation ofthis mass does not provide solid evidence of its identity. Other carriergases can be used to optimize the quantification of different mercuryspecies.

Isobutane to replace nitrogen as the chemical ionization (CI) gas was afirst choice, as it: 1) transfers less energy to the analyte, resultingin a “softer” ionization (i.e. less fragmentation) than nitrogen; 2)scavenges halide ions that may be produced by analyte fragmentation,preventing unwanted ion complexation; and 3) complexes with themolecular ion (M) in a consistent manner to form a [M+C₂H₂]⁻ ion. APCIanalysis with isobutane was initially performed at high concentrationsof CI gas (>1% isobutane in nitrogen) but tailing from the large peak atm/z=58 (isobutane) was significantly present in the baseline in theregion of interest for mercury halides (m/z=200-500).

For determining the optimal isobutene concentration, UHP nitrogen waspassed at 2 L/min through a 3 L glass flask containing 1 atm of 100%isobutane into a HgCl₂ source to the APCI-MS while monitoring the massspectrum at m/z=200-500. Under these conditions, the baseline decreasedby roughly a factor of 10 (2×10⁵ cts to ˜1×10⁴ cts) in the first 15minutes after the flask was opened, suggesting that decreasing theconcentration of isobutane to roughly 50 ppm would improve the detectionlimit for HgX₂ significantly. Between 15 minutes and 30 minutes thebaseline remained fairly constant, but the signal for HgCl₂ began todecrease as fragmentation by nitrogen increased. Operate with arelatively high concentration of isobutane (0.1% in nitrogen) was thenused to ensure complete fragmentation while allowing the freedom todilute down with UHP nitrogen to control the baseline intensity. At thisconcentration the tailing from isobutane may still be observed, but thetotal baseline intensity is still low (see FIG. 11).

b. Calibration

Gold and other nanoparticle-coated metal fibers were calibrated byinsertion into flasks containing the pure compounds of interest, fore.g. a single mercuric halide salt, either HgCl₂ or HgBr₂, under a 1atmosphere nitrogen headspace. At the temperatures of the laboratory,the headspaces of these flasks contained on the order of pmol HgX₂ perm³ of gas. Au-nanoparticle fibers/traps were exposed to the standardheadspace for a period of time consistent with respective airextractions. The fibers are then removed and stored in dry ice untilanalysis by APCI-MS, analogous to air extractions.

c. Calculation of Quantitative Results & Calibration and Determinationof Concentration

The quantification of mercuric halides, HgX₂ (X=Br, Cl, etc.) inwhole-air samples is based on the instrument response to knownquantities of pure analyte (i.e. standards) treated in an identicalmanner to the sample. For this method, this entails passing a gas with aknown concentration of HgX₂ through a gold trap for collection, followedby thermal desorption into the atmospheric pressure chemical ionizationmass spectrometer (APCI-MS) for detection. Ideally, this standard gaswould be passed through the gold trap for a length of time equivalent tothe sample collection, such that sample concentrations can be directlydetermined from the relative instrument responses. However, the longextraction times for whole-air samples make this method inconvenient forhigh-temporal-resolution atmospheric monitoring; a more accessiblemethod of calibration would focus on absolute calibration of molarquantities of analyte introduced to the APCI-MS. Once the absolutequantity of analyte desorbed from a trap is known, the total volume ofair passed through the trap and the trap collection efficiency may beused to accurately determine the original concentration in a whole-airsample.

Absolute calibration of the APCI-MS may be accomplished in severalmanners. In the first, a known quantity of gas containing a knownconcentration of HgX₂ is injected into an analyte-free gas stream thatenters the instrument. Varying the quantity of gas injected results inthe creation of a calibration curve that relates instrument response tothe molar quantity of analyte introduced to the instrument. A secondcalibration method, that more closely follows the whole-air samplingroutine, involves the passing of a known flux of HgX₂ standard throughthe gold trap used for sampling, in order to collect a known quantity ofanalyte in a short period of time. The flow rate may be adjusted using aflow meter and needle valve up-flow of the standard flask. The standardflask would consist of a multiple-stopcock-fitted glass flask containingsolid crystals of the analyte under a nitrogen headspace. The quantityof analyte exiting the flask over time is determined by the flow rate ofnitrogen passing through the flask and the vapour pressure of analyte inthe flask's headspace. After collection on the trap, the standard isthermally-desorbed into the instrument for detection. Varying the flowrate or the collection time, or mixing the standard stream with anotherstream of analyte-free nitrogen, can all be used to alter the quantityof analyte introduced into the instrument for calibration. As an addedbenefit, the collection efficiency of the trap may be directlydetermined by setting the standard flask and trap in-line with theinstrument during standard concentration on the trap, measuring thequantity of analyte that passes through the trap to the instrument, ifany.

d. Particulate Separation and Quantification

The flow tube inlets can be operated with and without Teflon™ filterswith diameters ranging from 0.1 micron to 2 microns. Hence the setup isused for identification of mercury compounds in the gas phase andparticulate manner.

e. Usage of Both Positive and Negative ion mass Spectrometry

The sensitivity of mass spectrometry for various mercury containingcompounds is not identical. FIGS. 12 a and 12 b are a few examplesshowing, for instance, that mercury halide species such as HgCl₂ arebest detected using the negative ionization mode, whereas compounds suchas HgO/Hg(OH)₂ are detected better using the positive ionization mode.

f. Advantages of Soft-Ionization for Mercury Quantitative Analysis inComparison to more Energetic (Harsh) Ionization

We performed a series of experiments in the laboratory to evaluate whichmass spectrometry instruments could provide more sensitive signals formercury containing species. As shown in FIG. 13, soft-ionizationtechniques (such as APCI-MS) are shown to be more sensitive and retainmore of the molecular ions of HgBr₂ than stronger ionization source,such as electron impact mass spectrometer (EI-MS).

g. Ambient Air and Water Matrices Measurements: Comparison with TotalRGM Data Results Indicating that:

-   -   A wide range of mercury species quantified and identified in air        and water    -   The technique is recyclable and a single trap/fiber can be used        several times and be recovered upon thermal desorption.

Time resolution average for most atmospheric measurement experiments areup to now currently 24 hours. We have performed experiments from 3 hoursto 3 days. The 24-hour averages are comparable or better than allexisting techniques that do not yield real chemical speciation.Quantification limits: Some examples of real mercury speciation in rangeof <20 ppt levels. Some examples for selected chemical speciationspecies in air are in FIGS. 14 a to c.

It is to be noted that there is a large natural variation (temporal andspatial) for mercury containing compounds, as it is the case for mostatmospheric chemical components. Based on our determination ofconcentrations, the concentrations when filters were not used, led toabout 80 ppt levels, which indicates that some reactive mercury might beassociated to particles.

It should be appreciated that the invention is not limited to theparticular embodiments described and illustrated herein but includes allmodifications and variations falling within the scope of the inventionas defined in the appended claims. For example, the present inventioncan be applied to other metals other than mercury. These other metalsmay also have different species and therefore also may be identified andquantified using the present invention.

REFERENCES

Every document, reference, patent, patent application publication,referred to below and/or throughout the application is herebyincorporated by reference in its entirety for all purposes.

1. Mercury fate and transport in the global atmosphere, Pirrone andMason, editors, Springer, pp, 459-501, ISBN: 987-0-387-93957-5 (2009).

2. P. A. Ariya, A. F. Khalizov, and A. Gidas, “Reaction of GaseousMercury with Atomic and Molecular Halogens: Kinetics, Product Studies,and Atmospheric Implications”, Journal of Physical Chemistry A, 106(32),7310-7320, (2002).

3. S. Coquet and P. Ariya, “The temperature dependence of Cl-atominitiated reactions of selected alkenes under tropospheric conditions”,International Journal of Chemical Kinetics, 32, 478-488, (2000).

1-29. (canceled)
 30. A portable device connectable to a speciationdevice for identifying and quantifying metal species in a sample, theportable device comprising a collection interface unit for collectingthe sample and concentrating an analyte.
 31. The portable device ofclaim 30, wherein the metal species are based on mercury, and compriseat least one species selected from HgBr₂, HgCl₂, HgI₂, HgCl, HgBr, HgI,HgO, Hg(OH)₂, and CH₃HgCl.
 32. The portable device of claim 30, whereinthe sample includes air, liquid, water, ice, or snow.
 33. The portabledevice of claim 30, wherein the collection interface unit includes atleast one collection interface comprising single layer or multi-layersof macro/micro/nano-particles, or a combination thereof; beads or wirecoated with macro/micro/nano-particles, or a combination thereof; a tubecoated with macro/micro/nano-particles; a tube containingmacro/micro/nano-particles beads, or wire, or a combination thereof;uncoated beads; uncoated wire; uncoated tube, or a combination thereof.34. The portable device of claim 33, wherein themacro/micro/nano-particles comprise gold- or sulfur-containingcompounds, or a combination thereof; and wherein the beads are glass ormetal.
 35. The portable device of claim 30, wherein the collectioninterface unit comprises a plurality of collection interfaces, whereinsaid interfaces are adapted for connection in parallel or in series. 36.The portable device of claim 30, wherein the collection interface unitcomprises a first and a second collection interface, the firstcollection interface comprising gold- or sulfur-containingmacro/micro/nano-particles or a mixture of gold- and sulfur-containingmacro/micro/nano-particles, and the second collection interfacecomprising uncoated glass beads.
 37. The portable device of claim 30,wherein the speciation device is selected from a mass spectrometer, anatmospheric pressure chemical ionization mass spectrometer, a softchemical ionization mass spectrometer, an electrospray ionization massspectrometer, a cold vapour atomic fluorescence spectrometer and anabsorption spectrometer.
 38. The portable device of claim 30, whereinthe speciation device is a modified speciation device and comprises adeactivated or passivated inner surface, and/or a decreased dead volumeinside an inlet.
 39. The portable device of claim 30, further comprisingat least one aerosol sizer or at least one filter for removingparticulates from the sample before the sample is collected.
 40. Asystem for identifying and quantifying metal species, the systemcomprising: a) a collection interface unit for collecting the sample andconcentrating an analyte; b) a soft ionization mass spectrometer; and c)a flow tube for connecting an outlet of the collection interface unit toan inlet of the soft ionization mass spectrometer.
 41. The system ofclaim 40, wherein the metal species are based on mercury, and compriseat least one species selected from HgBr₂, HgCl₂, HgI₂, HgCl, HgBr, HgI,HgO, Hg(OH)₂, and CH₃HgCl.
 42. The system of claim 40, wherein thesample includes air, liquid, water, ice, or snow.
 43. The system ofclaim 40, wherein the collection interface unit includes at least onecollection interface comprising single layer or multi-layers ofmacro/micro/nano-particles, or a combination thereof; beads or wirecoated with macro/micro/nano-particles, or a combination thereof; a tubecoated with macro/micro/nano-particles; a tube containingmacro/micro/nano-particles beads or wire, or a combination thereof;uncoated beads; uncoated wire; uncoated tube, or a combination thereof.44. The system of claim 40, wherein the macro/micro/nano-particlescomprise gold- or sulfur-containing compounds, or a combination thereof;and wherein the beads are glass or metal.
 45. The system of claim 40,wherein the collection interface unit comprises a plurality ofcollection interfaces, wherein said collection interfaces are adaptedfor connection in parallel or in series.
 46. The system of claim 40,wherein the collection interface unit comprises a first and a secondcollection interface, the first collection interface including gold- orsulfur-containing macro/micro/nano-particles or a mixture of gold- andsulfur-containing macro/micro/nano-particles, and the second collectioninterface including uncoated glass beads.
 47. The system of claim 40,wherein the soft ionization mass spectrometer is a modified softionization mass spectrometer having deactivated or passivated surfacesexposable to the sample, and/or a decreased dead volume inside an inlet.48. The system of claim 40, further comprising at least one aerosolsizer or at least one filter for removing particulates from the samplebefore the sample is collected.
 49. A system for identifying andquantifying metal species, the system comprising: a) a collectioninterface unit for collecting the sample and concentrating an analyte;b) a speciation device for identifying and quantifying the metal speciesfrom the analyte; and c) a flow tube for connecting an outlet of thecollection interface unit to an inlet of the speciation device.
 50. Thesystem of claim 49, wherein the speciation device is selected from amass spectrometer, soft chemical ionization mass spectrometer, anatmospheric pressure chemical ionization mass spectrometer, anelectrospray ionization mass spectrometer, a cold vapour atomicfluorescence spectrometer and an absorption spectrometer.
 51. The systemof claim 49, wherein the collection interface unit includes at least onecollection interface comprising single layer or multi-layers ofmacro/micro/nano-particles, or a combination thereof; beads or wirecoated with macro/micro/nano-particles, or a combination thereof; a tubecoated with macro/micro/nano-particles; a tube containingmacro/micro/nano-particles beads or wire, or a combination thereof;uncoated beads; uncoated wire; uncoated tube, or a combination thereof.52. The system of claim 51, wherein the macro/micro/nano-particlescomprise gold- or sulfur-containing compounds, or a combination thereof;and wherein the beads are glass or metal.
 53. A method for identifyingand quantifying metal species from a sample, the method comprising: a)collecting the sample onto a collection interface in a collectioninterface unit thereby concentrating an analyte; b) desorbing theanalyte; and c) identifying and quantifying the analyte's content inmetal species using a speciation device.
 54. The method of claim 53,wherein the metal species are based on mercury, and comprise at leastone species selected from HgBr₂, HgCl₂, HgI₂, HgCl, HgBr, HgI, HgO,Hg(OH)₂, and CH₃HgCl.
 55. The method of claim 53, wherein the sampleincludes air, liquid, water, ice, or snow.
 56. The method of claim 53,wherein the collection interface unit includes at least one collectioninterface comprising single layer or multi-layers ofmacro/micro/nano-particles, or a combination thereof; beads or wirecoated with macro/micro/nano-particles, or a combination thereof; a tubecoated with macro/micro/nano-particles; a tube containingmacro/micro/nano-particles beads or wire, or a combination thereof;uncoated beads; uncoated wire; uncoated tube, or a combination thereof.57. The method of claim 56, wherein the macro/micro/nano-particlescomprise gold- or sulfur-containing compounds, or a combination thereof;and wherein the beads are glass or metal.
 58. The method of claim 53,wherein step (a) comprises collecting the analyte on one collectioninterface comprising gold- or sulfur-containingmacro/micro/nano-particles or a mixture of gold- and sulphur-containingmacro/micro/nano-particles, and another collection interface comprisinguncoated glass beads.
 59. The method of claim 53, wherein step (a)comprises collecting the sample onto a plurality of collectioninterfaces connected in parallel or in series.
 60. The method of claim53, wherein the speciation device is selected from a mass spectrometer,a soft chemical ionization mass spectrometer, an atmospheric pressurechemical ionization mass spectrometer, an electrospray ionization massspectrometer, a cold vapour atomic fluorescence spectrometer or anabsorption spectrometer.
 61. The method of claim 53, wherein the methodincludes deactivating or passivating surfaces exposable to the sample inthe speciation device, and/or decreasing a dead volume inside an inletof the speciation device.
 62. The method of claim 53, further comprisingremoving particulates from the sample before collection on to thecollection interface.